EP1200408A2 - Bonding agent - Google Patents

Bonding agent

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Publication number
EP1200408A2
EP1200408A2 EP00958184A EP00958184A EP1200408A2 EP 1200408 A2 EP1200408 A2 EP 1200408A2 EP 00958184 A EP00958184 A EP 00958184A EP 00958184 A EP00958184 A EP 00958184A EP 1200408 A2 EP1200408 A2 EP 1200408A2
Authority
EP
European Patent Office
Prior art keywords
hydroxyquinoline
organic
ppm
group
adhesion promoter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00958184A
Other languages
German (de)
French (fr)
Other versions
EP1200408B1 (en
Inventor
Marlies HÜLSEBUSCH
Jürgen Lindner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atlas Elektronik GmbH
Original Assignee
STN Atlas Elektronik GmbH
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Publication date
Application filed by STN Atlas Elektronik GmbH filed Critical STN Atlas Elektronik GmbH
Publication of EP1200408A2 publication Critical patent/EP1200408A2/en
Application granted granted Critical
Publication of EP1200408B1 publication Critical patent/EP1200408B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/166—Metal in the pretreated surface to be joined

Definitions

  • the present invention relates to 8-hydroxyquinoline derivatives, production processes for 8-hydroxyquinoline derivatives and their use as adhesion promoters between metallic surfaces and organic polymer layers.
  • metallic surfaces and organic polymer layers In particular, iron alloys and ceramic surfaces coated with silver or gold, e.g. Piezoceramics.
  • Polyurethanes are particularly suitable as the organic polymer layer, e.g. Adhesives and varnishes.
  • the organic polymer layer can be applied from an organic solution or an aqueous dispersion of the paint or adhesive components, which polymerize completely only on the adhesion promoter layer.
  • adhesion promoters also called primers, such as Zinc chromate primers are toxic due to their heavy metal content and are therefore harmful to the environment.
  • the task is to provide a toxicologically harmless and environmentally compatible adhesion promoter which contains organic polymer layers such as e.g. Paint and adhesive layers can firmly connect to metallic surfaces.
  • the object of the present invention is to find a process for producing suitable adhesion promoters which is capable of producing a sufficiently high reaction yield with a few reaction steps, so that no extensive purification or isolation steps are required to obtain the adhesion promoter from the reaction mixture.
  • the solution according to the invention is provided by modifying 8-hydroxyquinoline with organic diazonium compounds. It has been found that 8-hydroxyquinoline derivatives are particularly suitable as adhesion promoters if they carry a substituent which is connected via an azo coupling and which carries a group which is capable of reacting with components of the organic polymer layer to be applied.
  • an adhesion promoter based on 8-hydroxyquinoline derivatives can in principle be broken down chemically or biologically into harmless products.
  • 8-Hydroxyquinoline also known as 8-quinolinol or oxin, is used in medicine as a fungicide and antiseptic, in analytics as an organic complexing agent for more than 40
  • adhesion promoters according to the invention show a very high moisture resistance and good corrosion protection properties in connection with the polymer composite. These adhesion promoters also have only a low toxicity. For the application of the adhesion promoters to the surfaces to be coated, only a slight temperature influence is exerted on the substrate and, moreover, the order is highly constant or reproducible.
  • the azo coupling of an organic substituent bearing a polymer-specific group to the 8-hydroxyquinoline can be achieved by means of the corresponding diazonium compound of the substituent.
  • the diazonium compound of the organic substituent which carries another reactive polymer-specific group can be obtained by reacting the corresponding amine compound with nitrite, e.g. Sodium nitrite.
  • R reactive group, especially amino, carboxy, epoxy or vinyl group.
  • the benzene ring in the substituent, it is also possible to use other organic radicals which act as a spacer molecule. In the general reaction scheme shown here, the benzene ring also serves as a spacer. Alkenyl radicals having 2 to 6 carbon atoms, such as ethenyl, propenyl, butenyl, pentenyl and hexenyl, can also be used as spacers.
  • Substituents that have more than one reactive group can also be connected to the 8-hydroxyquinoline via an azo coupling.
  • FIG. 1 shows the FT-IR drift spectrum of an adhesion promoter based on 8-hydroxyquinoline.
  • Figure 2 shows the FT-IR spectrum of the adhesion promoter, applied to silver plate.
  • FIG. 3 shows the FT-IR drift spectrum of an adhesion promoter based on 8-hydroxyquinoline.
  • Figure 4 shows the FT-IR spectrum of the coupling agent after application to a gold-plated stainless steel sheet.
  • FIGS. 5 and 6 show the structure of a coating on metallic surfaces 1.5 composed of adhesion promoter 2.4 and organic polymer 3.
  • FIG. 7 shows structural formulas of adhesion promoters according to the invention.
  • the mixture is stirred at this temperature for a further 2 hours, then the mixture is allowed to warm up slowly to room temperature. Part of the product is already failing. Complete precipitation is achieved by carefully neutralizing with cooling achieved with aqueous ammonia solution. The precipitated product is filtered off and washed with ice water.
  • the decomposition temperature is 273 ° C.
  • the IR spectrum shows the following peaks: 3005, 2865, 1630, 1605, 1550, 1505, 1400, 1375, 1350, 1300, 1235, 1080, 850 cm "1.
  • 1 H NMR spectrum (250 MHz, DMSO, downfield shift against TMS): 9.33 ppm (1 H), 8.99 ppm (1 H), 8.03 ppm (1 H), 8.02 ppm (2 H), 7.77 ppm (1 H), 7, 71 ppm (2 H), 7.25 ppm (1 H), 4.14 ppm (2 H).
  • the melting point is 221 ° C.
  • the IR spectrum shows the following peaks: 3290, 3065, 2920, 2865, 1570, 1475, 1280, 1225, 1190, 1020, 845, 790, 710 cm "1st ⁇ NMR spectrum (250 MHz, DMSO, downfield shift against TMS): 9.31 ppm (1 H), 9.00 ppm (1 H), 8.01 ppm (1 H), 7.97 ppm (2 H), 7.76 ppm (1 H), 7, 56 ppm (2 H), 7.26 ppm (1 H).
  • the melting point is> 300 ° C.
  • IR spectrum 3350, 3190, 3030, 2920 1740, 1690, 1600, 1580, 1410, 1340, 1270, 1165, 940, 790, 670 cm "1.
  • 1H NMR spectrum (250 MHz, DMSO, downfield shift against TMS ): 9.33 ppm (1 H), 9.00 ppm (1 H), 8.02 ppm (2 H), 7.92 ppm (1 H), 7.75 ppm (1 H), 7.70 ppm (2 H), 7.23 ppm (1 H), 6.86 ppm (1 H), 6.00 ppm (1 H), 5.40 ppm (1 H).
  • adhesion promoters according to the invention can be applied to a metallic surface in an ethanolic solution.
  • the complexation of the metallic surface by adhesion promoters based on 8-hydroxyquinoline according to the invention is clear in the following examples:
  • Example 4 Coating a silver surface with an adhesion promoter based on 8-hydroxyquinoline
  • Gold-plated brass sheet was coated with 25 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, in an immersion bath for 24 hours. Silver-filled epoxy adhesive was then applied and the tensile shear strength after curing and conditioning the bond at room temperature was determined to be 9.9 N / mm in accordance with DIN EN1465. WO 01/09099. g. PCT / DE00 / 02481
  • Gold-plated brass sheet was coated with 5 mg of 5- (p-aminobenzylazo) -8-hydroxyquinoline, dissolved in 200 ml of ethanol, by immersion for 24 hours. Subsequently, silver-filled epoxy adhesive was applied and the tensile strength after evaluation and conditioning of the bond in accordance with DIN EN 1465 at room temperature was found to be 9.5 N / mm 2 .
  • AlMg 3 was coated with 20 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, by immersion for 23 hours.
  • Polyurethane casting resin for example Biresin 1305, was then applied and the tensile strength was measured after evaluating and conditioning the bond by determining the tensile strength of two round specimens with a diameter of 20 mm glued to one another with the end faces.
  • the test at room temperature showed a tensile strength of 8 N / mm, after aging in water at a temperature above 95 ° C for 16 hours a value of 4.3 N / mm 2 , again measuring at room temperature.
  • Stainless steel No. 1.4571 was coated with 20 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, by immersion for 23 hours.
  • Polyurethane casting resin for example Biresin U1305, was then applied and the tensile strength was measured as in Example 9 after the bond had hardened and was conditioned. The measurement at room temperature showed a tensile strength of 5.1 N / mm 2 , the tensile strength after aging in water at a temperature above 95 ° C for 16 hours a tensile strength of 6.1 N / mm 2 , again measured at room temperature.
  • Example 11 Tensile test on silver-coated ceramic
  • Example 10 A 10 mm silver coated ceramic was coated with 5- (p-vinylbenzylazo) -8-hydroxyquinoline as shown in Example 10. After curing and conditioning the bond with polyurethane casting resin, the tensile strength was measured as in Example 9. At room temperature there was a strength value of 4 N / mm 2 , after aging in water at a temperature above 95 ° C for 16 hours a strength value of 1.6 N / mm 2 , again measured at room temperature.
  • Example 10 A 10 mm silver-coated ceramic was coated with 5- (p-aminobenzylazo) -8-hydroxyquinoline as shown in Example 10.
  • the tensile strength of the polyurethane cast resin was measured after curing and conditioning the bond, as shown in Example 9.
  • the tensile strength test at room temperature gave a value of 5.2 N / mm 2 ; after aging in water at a temperature above 95 ° C for 16 hours a value of 2.2 N / mm, again measured at room temperature.
  • the adhesion promoters according to the invention can be applied in a very small layer thickness, i.e. if necessary, be applied to the metallic surface in a monomolecular layer.
  • the successive layers namely the adhesion promoter according to the invention directly on a metallic surface, a polymer layer reacting with the reactive polymer-specific group of the adhesion promoter can in turn be coated with a layer of the adhesion promoter according to the invention, which is layered on a metallic surface, when building up an electronic component.
  • FIGS. 5 and 6 results.
  • layer 1 is a metallic surface
  • layer 2 is the adhesion promoter layer
  • layer 3 is an organic polymer layer.
  • layer 1 is a metallic layer
  • layer 2 is the adhesion promoter layer
  • layer 3 is an organic polymer layer
  • layer 4 is another adhesion promoter layer
  • layer 5 is another metallic layer.
  • the layers 1 in Figures 5 and 6 can also be a thin metal layer which has been applied to a base, e.g. a gold or silver coating on a piezo ceramic.
  • FIG. 6 shows a structure in which two identical or different metallic surfaces, layers 1 and 5, are each covered with a layer of the adhesion promoter which adjoins a common organic polymer layer on opposite sides.
  • the adhesion promoter layers 2 and 4 can consist of the same 8-hydroxyquinoline derivative, or of different ones, as long as they only carry reactive groups that can react with mono- or oligomeric organic polymer layer 3.
  • the organic polymer layer 3 here can be a mixture of different monomers, e.g. Monomers that can form polyesters, polyurethanes, polycarbonates and / or polyamides.

Abstract

The invention relates to 8-hydroxychinoline derivatives, methods for preparing 8-hydroxychinoline derivatives and their use as a bonding agent between metallic surfaces and organic polymer layers. The inventive 8-hydroxychinoline derivatives are capable of bonding organic polymer layers to metallic surfaces.

Description

WO 01/09099 . i . PCT/DE00/024 1 WO 01/09099. i. PCT / DE00 / 024 1
Haftvermittlerbonding agent
Die vorliegende Erfindung bezieht sich auf 8-Hydroxychinolinderivate, Herstellungsverfahren für 8-Hydroxychinolinderivate und deren Verwendung als Haftvermittler zwischen metallischen Oberflächen und organischen Polymerschichten. Als metallische Oberflächen kommen insbesondere Eisenlegierungen und mit Silber oder Gold beschichtete Keramikoberflächen, z.B. Piezokeramiken, in Betracht. Als organische Polymerschicht kommen insbesondere Polyurethane in Betracht, z.B. Klebstoffe und Lacke. Die organische Polymerschicht kann bei Verwendung des erfindungsgemäßen Haftvermittlers aus einer organischen Lösung oder einer wäßrigen Dispersion der Lack- oder Klebstoffbestandteile aufgebracht werden, die erst auf der Haftvermittlerschicht vollständig auspolymerisieren.The present invention relates to 8-hydroxyquinoline derivatives, production processes for 8-hydroxyquinoline derivatives and their use as adhesion promoters between metallic surfaces and organic polymer layers. In particular, iron alloys and ceramic surfaces coated with silver or gold, e.g. Piezoceramics. Polyurethanes are particularly suitable as the organic polymer layer, e.g. Adhesives and varnishes. When using the adhesion promoter according to the invention, the organic polymer layer can be applied from an organic solution or an aqueous dispersion of the paint or adhesive components, which polymerize completely only on the adhesion promoter layer.
Bisher verwendete Haftvermittler, auch Primer genannt, wie z.B. Zink-Chromat-Primer, sind aufgrund ihres Schwermetallgehaltes toxisch und daher auch für die Umwelt schädlich. Die Aufgabe besteht vorliegend darin, einen toxikologisch unbedenklichen und umweltverträglichen Haftvermittler bereitzustellen, der organische Polymerschichten wie z.B. Lack- und Klebstoffschichten fest mit metallischen Oberflächen verbinden kann. Weiterhin stellt sich vorliegend die Aufgabe, eine Verfahren zur Herstellung geeigneter Haftvermittler aufzufinden, das in der Lage ist, mit wenigen Reaktionsschritten eine ausreichend hohe Reaktionsausbeute zu ergeben, so daß keine umfangreichen Aufreinigungs- oder Isolierungsschritte zur Gewinnung des Haftvermittlers aus der Reaktionsmischung erforderlich sind.Previously used adhesion promoters, also called primers, such as Zinc chromate primers are toxic due to their heavy metal content and are therefore harmful to the environment. In the present case, the task is to provide a toxicologically harmless and environmentally compatible adhesion promoter which contains organic polymer layers such as e.g. Paint and adhesive layers can firmly connect to metallic surfaces. Furthermore, the object of the present invention is to find a process for producing suitable adhesion promoters which is capable of producing a sufficiently high reaction yield with a few reaction steps, so that no extensive purification or isolation steps are required to obtain the adhesion promoter from the reaction mixture.
Die erfindungsgemäße Lösung wird durch die Modifizierung von 8-Hydroxychinolin mit organischen Diazoniumverbindungen bereitgestellt. Es wurde gefunden, daß 8-Hydroxy- chinolinderivate dann besonders als Haftvermittler geeignet sind, wenn sie einen Substituen- ten tragen, der über eine Azokupplung verbunden ist und der eine Gruppe trägt, die zur Reaktion mit Komponenten der aufzubringenden organischen Polymerschicht fähig ist.The solution according to the invention is provided by modifying 8-hydroxyquinoline with organic diazonium compounds. It has been found that 8-hydroxyquinoline derivatives are particularly suitable as adhesion promoters if they carry a substituent which is connected via an azo coupling and which carries a group which is capable of reacting with components of the organic polymer layer to be applied.
Ein Haftvermittler auf Basis von 8-Hydroxychinolinderivaten ist als organisches Produkt prinzipiell chemisch oder biologisch zu unschädlichen Produkten abbaubar. 8-Hydroxychinolin, auch bekannt als 8-Chinolinol oder Oxin, ist in der Medizin als Fungizid und Antiseptikum, in der Analytik als organischer Komplexbildner für mehr als 40 verschieAs an organic product, an adhesion promoter based on 8-hydroxyquinoline derivatives can in principle be broken down chemically or biologically into harmless products. 8-Hydroxyquinoline, also known as 8-quinolinol or oxin, is used in medicine as a fungicide and antiseptic, in analytics as an organic complexing agent for more than 40
dene Metalle bekannt. Es ist bisher jedoch noch nicht vorgeschlagen worden, Haftvermittler für Klebstoff- oder Lackschichten, die auf eine metallische Oberfläche aufgebracht werden sollen, auf Basis von 8-Hydroxychinolin bereitzustellen. Weiterhin wurde bisher kein Verfahren zur Herstellung von 8-Hydroxychinolinderivaten zur Verfügung gestellt, das mit wenigen Reaktionsschritten eine hohe Reaktionsausbeute ergibt.known metals. However, it has not yet been proposed to provide adhesion promoters for adhesive or lacquer layers, which are to be applied to a metallic surface, on the basis of 8-hydroxyquinoline. Furthermore, no process for the preparation of 8-hydroxyquinoline derivatives has been made available which results in a high reaction yield with only a few reaction steps.
Die erfindungsgemäßen Haftvermittler zeigen eine sehr hohe Feuchtigkeitsbeständigkeit und gute Korrosionsschutzeigenschaften im Zusammenhang mit dem Polymerverbund. Diese Haftvermittler weisen überdies eine nur geringe Toxizität auf. Für den Auftrag der Haftvermittler auf die zu beschichtenden Oberflächen wird nur ein geringer Temperatureinfluß auf die Unterlage ausgeübt und überdies eine hohe Konstanz bzw. Reproduzierbarkeit des Auftrages erzielt.The adhesion promoters according to the invention show a very high moisture resistance and good corrosion protection properties in connection with the polymer composite. These adhesion promoters also have only a low toxicity. For the application of the adhesion promoters to the surfaces to be coated, only a slight temperature influence is exerted on the substrate and, moreover, the order is highly constant or reproducible.
Die Azokupplung eines organischen Substituenten, der eine polymerspezifische Gruppe trägt, an das 8-Hydroxychinolin kann mittels der entsprechenden Diazoniumverbindung des Substituenten erzielt werden. Die Diazoniumverbindung des organischen Substituenten, der eine weitere reaktive polymerspezifische Gruppe trägt, läßt sich durch Umsetzen der entsprechenden Aminverbindung mit Nitrit, z.B. Natriumnitrit, erreichen.The azo coupling of an organic substituent bearing a polymer-specific group to the 8-hydroxyquinoline can be achieved by means of the corresponding diazonium compound of the substituent. The diazonium compound of the organic substituent which carries another reactive polymer-specific group can be obtained by reacting the corresponding amine compound with nitrite, e.g. Sodium nitrite.
Das allgemeine Reaktionsschema für die Azokupplung des Substituenten, der eine reaktive polymerspezifische Gruppe trägt, an das 8-Hydroxychinolin erfolgt nach dem allgemeinen Reaktionsschema: The general reaction scheme for the azo coupling of the substituent, which carries a reactive polymer-specific group, to the 8-hydroxyquinoline is carried out according to the general reaction scheme:
R = reaktive Gruppe, insbesondere Amino-, Carboxy-, Epoxy- oder Vinylgruppe.R = reactive group, especially amino, carboxy, epoxy or vinyl group.
Anstelle des Benzolringes im Substituenten lassen sich auch andere organische Reste verwenden, die als Spacermolekül fungieren. Im hier gezeigten allgemeinen Reaktionsschema dient der Benzolring gleichzeitig als Spacer. Als Spacer können auch Alkenylreste mit 2 bis 6 Kohlenstoffatomen dienen, wie Ethenyl, Propenyl, Butenyl, Pentenyl und Hexenyl.Instead of the benzene ring in the substituent, it is also possible to use other organic radicals which act as a spacer molecule. In the general reaction scheme shown here, the benzene ring also serves as a spacer. Alkenyl radicals having 2 to 6 carbon atoms, such as ethenyl, propenyl, butenyl, pentenyl and hexenyl, can also be used as spacers.
Es können auch Substituenten über eine Azokupplung mit dem 8-Hydroxychinolin verbunden werden, die mehr als nur eine reaktive Gruppe aufweisen.Substituents that have more than one reactive group can also be connected to the 8-hydroxyquinoline via an azo coupling.
Die Azokupplung des Diazoniumsubstituenten erfolgt fast ausschließlich in 5-Stellung des 8- Hydroxychinolins.The azo coupling of the diazonium substituent takes place almost exclusively in the 5-position of the 8-hydroxyquinoline.
Die vorliegende Erfindung wird anhand der nachfolgenden Beispiele näher erläutert, die jedoch nicht als Beschränkung aufzufassen sind. Kurze Beschreibung der Figuren:The present invention is explained in more detail with reference to the following examples, which, however, are not to be understood as a limitation. Brief description of the figures:
Figur 1 zeigt das FT-IR-Drift-Spektrum eines Haftvermittlers auf Basis von 8-Hydroxychino- lin.FIG. 1 shows the FT-IR drift spectrum of an adhesion promoter based on 8-hydroxyquinoline.
Figur 2 zeigt das FT-IR-Spektrum des Haftvermittlers, auf Silberblech aufgetragen.Figure 2 shows the FT-IR spectrum of the adhesion promoter, applied to silver plate.
Figur 3 zeigt das FT-IR-Drift-Spektrum eines Haftvermittlers auf Basis von 8-Hydroxychino- lin.FIG. 3 shows the FT-IR drift spectrum of an adhesion promoter based on 8-hydroxyquinoline.
Figur 4 zeigt das FT-IR-Spektrum des Haftvermittlers nach Auftragen auf ein vergoldetes Edelstahlblech.Figure 4 shows the FT-IR spectrum of the coupling agent after application to a gold-plated stainless steel sheet.
Figuren 5 und 6 zeigen den Aufbau einer Beschichtung auf metallischen Oberflächen 1,5 aus Haftvermittler 2,4 und organischem Polymer 3.FIGS. 5 and 6 show the structure of a coating on metallic surfaces 1.5 composed of adhesion promoter 2.4 and organic polymer 3.
Figur 7 zeigt Strukturformeln erfindungsgemäßer Haftvermittler.FIG. 7 shows structural formulas of adhesion promoters according to the invention.
Beispiel 1 : Synthese von 5-(p-Aminobenzylazo)-8-hydroxychinolinExample 1: Synthesis of 5- (p-aminobenzylazo) -8-hydroxyquinoline
2,44 g (0,02 Mol) p-Aminobenzylamin werden in eine Mischung aus 9 ml (0,1 Mol) einer 37%igen Salzsäure und 35 ml Wasser gegeben. Die Lösung wird auf 0-5°C gekühlt. Die Dia- zotierung wird durch Zugabe einer Lösung aus 1,38 g (0,02 Mol) NaN02 in 10 ml Wasser gestartet. Anschließend wird für 30 Minuten bei Raumtemperatur gerührt. Diese Lösung aus diazotiertem p-Aminobenzylamin wird langsam zu einer kalten Lösung (0-5 °C) aus 2,90 g 8- Hydroxychinolin in 80%iger Essigsäurelösung getropft, so daß die Temperatur nicht über 5°C ansteigt. Nach vollständiger Zugabe wird für weitere 2 Stunden bei dieser Temperatur gerührt, dann läßt man langsam auf Raumtemperatur erwärmen. Dabei fällt bereits ein Teil des Produktes aus. Die vollständige Fällung wird durch vorsichtiges Neutralisieren unter Kühlung mit wäßriger Ammoniaklösung erreicht. Das ausgefällte Produkt wird abgenutscht und mit Eiswasser gewaschen.2.44 g (0.02 mol) of p-aminobenzylamine are added to a mixture of 9 ml (0.1 mol) of 37% hydrochloric acid and 35 ml of water. The solution is cooled to 0-5 ° C. The diazo is started by adding a solution of 1.38 g (0.02 mol) of NaNO 2 in 10 ml of water. The mixture is then stirred at room temperature for 30 minutes. This solution of diazotized p-aminobenzylamine is slowly added dropwise to a cold solution (0-5 ° C.) of 2.90 g of 8-hydroxyquinoline in 80% acetic acid solution, so that the temperature does not rise above 5 ° C. After the addition is complete, the mixture is stirred at this temperature for a further 2 hours, then the mixture is allowed to warm up slowly to room temperature. Part of the product is already failing. Complete precipitation is achieved by carefully neutralizing with cooling achieved with aqueous ammonia solution. The precipitated product is filtered off and washed with ice water.
Die Zersetzungstemperatur beträgt 273°C. Das IR-Spektrum zeigt folgende Peaks: 3005, 2865, 1630, 1605, 1550, 1505, 1400, 1375, 1350, 1300, 1235, 1080, 850 cm"1. 1H-NMR- Spektrum (250 MHz, DMSO, Tieffeldverschiebung gegen TMS): 9,33 ppm (1 H), 8,99 ppm (1 H), 8,03 ppm (1 H), 8,02 ppm (2 H), 7,77 ppm ( 1 H ), 7,71 ppm (2 H), 7,25 ppm (1 H), 4,14 ppm (2 H).The decomposition temperature is 273 ° C. The IR spectrum shows the following peaks: 3005, 2865, 1630, 1605, 1550, 1505, 1400, 1375, 1350, 1300, 1235, 1080, 850 cm "1. 1 H NMR spectrum (250 MHz, DMSO, downfield shift against TMS): 9.33 ppm (1 H), 8.99 ppm (1 H), 8.03 ppm (1 H), 8.02 ppm (2 H), 7.77 ppm (1 H), 7, 71 ppm (2 H), 7.25 ppm (1 H), 4.14 ppm (2 H).
Beispiel 2: Synthese von 5-(p-Hvdroxybenzylazo)-8-hvdroxychinolinExample 2: Synthesis of 5- (p-Hvdroxybenzylazo) -8-hvdroxyquinoline
2,46 g (0,02 Mol) 4-Aminobenzylalkohol werden in einer Mischung aus 5 ml konzentrierter HC1 und 100 ml Wasser gelöst, auf 0-5 °C gekühlt und mit 1,38 g (0,02 Mol) NaN02 in 10 ml Wasser diazotiert. 2,90 g (0,02 Mol) 8-Hydroxychinolin werden in 10 ml 1 M NaOH gelöst und auf 0-5 °C gekühlt. Dieser Lösung wird langsam die Lösung des diazotierten 4- Aminobenzylalkohols zugegeben. Es wird für weitere 16 Stunden bei dieser Temperatur rühren gelassen. Anschließend wird mit konzentrierter Essigsäure neutralisiert und das enstande- nen Produkt abgenutscht.2.46 g (0.02 mol) of 4-aminobenzyl alcohol are dissolved in a mixture of 5 ml of concentrated HC1 and 100 ml of water, cooled to 0-5 ° C and with 1.38 g (0.02 mol) of NaN0 2 in 10 ml of water diazotized. 2.90 g (0.02 mol) of 8-hydroxyquinoline are dissolved in 10 ml of 1 M NaOH and cooled to 0-5 ° C. The solution of the diazotized 4-aminobenzyl alcohol is slowly added to this solution. It is allowed to stir at this temperature for a further 16 hours. It is then neutralized with concentrated acetic acid and the product formed is filtered off with suction.
Der Schmelzpunkt beträgt 221°C. Das IR-Spektrum zeigt folgende Peaks: 3290, 3065, 2920, 2865, 1570, 1475, 1280, 1225, 1190, 1020, 845, 790, 710 cm"1. Η-NMR- Spektrum (250 MHz, DMSO, Tieffeldverschiebung gegen TMS): 9,31 ppm (1 H), 9,00 ppm (1 H), 8,01 ppm (1 H), 7,97 ppm (2 H), 7,76 ppm (1 H), 7,56 ppm (2 H), 7,26 ppm (1 H).The melting point is 221 ° C. The IR spectrum shows the following peaks: 3290, 3065, 2920, 2865, 1570, 1475, 1280, 1225, 1190, 1020, 845, 790, 710 cm "1st Η NMR spectrum (250 MHz, DMSO, downfield shift against TMS): 9.31 ppm (1 H), 9.00 ppm (1 H), 8.01 ppm (1 H), 7.97 ppm (2 H), 7.76 ppm (1 H), 7, 56 ppm (2 H), 7.26 ppm (1 H).
13C-NMR-Spektrum (62,9 MHz, Tieffeldverschiebung gegen TMS): 157.3 ppm, 151 ,5 ppm, 148,9 ppm, 145,5 ppm, 138,6 ppm. 137,9 ppm, 131,7 ppm. 127,4 ppm, 127,1 ppm, 123,0 ppm, 122.3 ppm, 114,6 ppm. 111.6 ppm. 62,5 ppm. Beispiel 3: Synthese von 5-(p-Vinylbenzylazo)-8-hydroxychinolin 13 C-NMR spectrum (62.9 MHz, downfield shift against TMS): 157.3 ppm, 151, 5 ppm, 148.9 ppm, 145.5 ppm, 138.6 ppm. 137.9 ppm, 131.7 ppm. 127.4 ppm, 127.1 ppm, 123.0 ppm, 122.3 ppm, 114.6 ppm. 111.6 ppm. 62.5 ppm. Example 3: Synthesis of 5- (p-vinylbenzylazo) -8-hydroxyquinoline
2,98 g (0,025 Mol) p-Vinylanilin werden in 5 ml konzentrierter HC1 in 100 ml Wasser gelöst. Die Lösung wird auf 0-5°C gekühlt und mit 1,73 g (0,025 Mol) NaN02 in 12 ml Wasser dia- zotiert. Diese Diazoniumlösung wird langsam zu einer kalten Lösung von 3,7 g (0,025 Mol) 8-Hydroxychinolin in 50 ml 2-Ethoxyethanol und einer Lösung aus 1 g NaOH sowie 5 g Na C03 in 50 ml Wasser gegeben. Die Lösung wird anschließend für 24 Stunden bei 0-5°C gerührt. Der ausgefallene Feststoff wird abgenutscht und mit Eiswasser gewaschen. Der Feststoff wird in Methanol umkristallisiert.2.98 g (0.025 mol) of p-vinylaniline are dissolved in 5 ml of concentrated HCl in 100 ml of water. The solution is cooled to 0-5 ° C and diazotized with 1.73 g (0.025 mol) NaN0 2 in 12 ml water. This diazonium solution is slowly added to a cold solution of 3.7 g (0.025 mol) of 8-hydroxyquinoline in 50 ml of 2-ethoxyethanol and a solution of 1 g NaOH and 5 g Na CO 3 in 50 ml water. The solution is then stirred at 0-5 ° C for 24 hours. The precipitated solid is filtered off and washed with ice water. The solid is recrystallized from methanol.
Der Schmelzpunkt liegt bei >300°C. IR-Spektrum: 3350, 3190, 3030, 2920 1740, 1690, 1600, 1580, 1410, 1340, 1270, 1165, 940, 790, 670 cm"1. 1H-NMR-Spektπιm (250 MHz, DMSO, Tieffeldverschiebung gegen TMS): 9,33 ppm (1 H), 9,00 ppm (1 H), 8,02 ppm (2 H), 7,92 ppm (1 H), 7,75 ppm (1 H), 7,70 ppm (2 H), 7,23 ppm (1 H), 6,86 ppm (1 H), 6,00 ppm (1 H), 5,40 ppm (1 H).The melting point is> 300 ° C. IR spectrum: 3350, 3190, 3030, 2920 1740, 1690, 1600, 1580, 1410, 1340, 1270, 1165, 940, 790, 670 cm "1. 1H NMR spectrum (250 MHz, DMSO, downfield shift against TMS ): 9.33 ppm (1 H), 9.00 ppm (1 H), 8.02 ppm (2 H), 7.92 ppm (1 H), 7.75 ppm (1 H), 7.70 ppm (2 H), 7.23 ppm (1 H), 6.86 ppm (1 H), 6.00 ppm (1 H), 5.40 ppm (1 H).
Die erfindungsgemäßen Haftvermittler können ethanolischer Lösung auf eine metallische Oberfläche aufgebracht werden. Die Komplexierung der metallischen Oberfläche durch erfindungsgemäßer Haftvermittler auf Basis von 8-Hydroxychinolin wird in den folgenden Beispielen deutlich:The adhesion promoters according to the invention can be applied to a metallic surface in an ethanolic solution. The complexation of the metallic surface by adhesion promoters based on 8-hydroxyquinoline according to the invention is clear in the following examples:
Beispiel 4: Beschichtung einer Silberoberfläche mit Haftvermittler auf der Basis von 8- HydroxychinolinExample 4: Coating a silver surface with an adhesion promoter based on 8-hydroxyquinoline
Der Vergleich der IR-Spektren eines Haftvermittlers auf Basis von 8-Hydroxychinolin, in Figur 1 dargestellt, mit dem auf Silberblech aufgetragenen Haftvermittler, in Figur 2 dargestellt, zeigt, daß die OH-Schwingung des Haftvermittlers nicht mehr auftritt, wenn er auf die Silberoberfläche aufgetragen ist. Beispiel 5: Beschichtung einer Goldoberfläche mit einem Haftvermittler auf Basis von 8- HydroxychinolinThe comparison of the IR spectra of an adhesion promoter based on 8-hydroxyquinoline, shown in FIG. 1, with the adhesion promoter applied to silver sheet, shown in FIG. 2, shows that the OH vibration of the adhesion promoter no longer occurs when it hits the silver surface is applied. Example 5: Coating a gold surface with an adhesion promoter based on 8-hydroxyquinoline
Der Vergleich der IR-Spektren eines erfindungsgemäßen Haftvermittlers, in Figur 3 dargestellt, und des auf vergoldetes Edelstahlblech aufgetragenen Haftvermittlers, in Figur 4 zeigt, daß die OH-Schwingung des Haftvermittlers nach Auftragen auf die Goldoberfläche nicht mehr vorliegt. Das Fehlen dieser OH-Schwingung belegt die Komplexbildung des erfindungsgemäßen Haftvermittlers mit der Goldoberfläche.The comparison of the IR spectra of an adhesion promoter according to the invention, shown in FIG. 3, and the adhesion promoter applied to gold-plated stainless steel sheet, in FIG. 4, shows that the OH vibration of the adhesion promoter is no longer present after application to the gold surface. The absence of this OH vibration proves the complex formation of the adhesion promoter according to the invention with the gold surface.
Beispiel 6: Zugfestigkeitsprobe auf CrNil810Example 6: Tensile strength test on CrNil810
Für die Zugfestigkeitsprobe nach DIN 53281 wurde CrNil810 mit 25 mg 5-p- (Aminobenzylazo)-8-hydroxychinolin, gelöst in 250 ml Ethanol, durch Tauchen während 12 Stunden beschichtet. Anschließend wurde Epoxidklebstoff, Typ 9323 der Firma 3M aufgebracht und die Zugverfestigkeit nach Aushärtung und Konditionierung der Klebung gemes- sen. Bei Raumtemperatur ergab sich ein Wert von 19 N/mm , nach einer Auslagerung von 16 Stunden in Wasser bei über 95 °C eine Wert von 19 N/mm , wiederum bei Raumtemperatur gemessen.For the tensile strength test according to DIN 53281, CrNil810 was coated with 25 mg of 5-p- (aminobenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, by immersion for 12 hours. Epoxy adhesive, type 9323 from 3M, was then applied and the tensile strength was measured after the adhesive had hardened and been conditioned. A value of 19 N / mm resulted at room temperature, and after exposure for 16 hours in water at over 95 ° C. a value of 19 N / mm, again measured at room temperature.
Beispiel 7: Zugscherfestigkeitsprobe auf vergoldetem MessingblechExample 7: Tensile shear strength test on gold-plated brass sheet
Vergoldetes Messingblech wurde mit 25 mg 5-(p-Vinylbenzylazo)-8-hydroxychinolin, in 250 ml Ethanol gelöst, im Tauchbad über 24 Stunden beschichtet. Anschließend wurde silbergefüllter Epoxidklebstoff aufgetragen und die Zugscherfestigkeit nach Aushärtung und Konditionierung der Klebung bei Raumtemperatur gemäß DIN EN1465 zu 9,9 N/mm bestimmt. WO 01/09099 . g . PCT/DE00/02481Gold-plated brass sheet was coated with 25 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, in an immersion bath for 24 hours. Silver-filled epoxy adhesive was then applied and the tensile shear strength after curing and conditioning the bond at room temperature was determined to be 9.9 N / mm in accordance with DIN EN1465. WO 01/09099. g. PCT / DE00 / 02481
Beispiel 8: Zugscherfestigkeitsprobe auf vergoldetem MessingblechExample 8: Tensile shear strength test on gold-plated brass sheet
Vergoldetes Messingblech wurde mit 5 mg 5-(p-Aminobenzylazo)-8-hydroxychinolin, in 200 ml Ethanol gelöst, durch Tauchen für 24 Stunden beschichtet. Anschließend wurde silbergefüllter Epoxidklebstoff aufgetragen und die Zugverfestigkeit nach Auswertung und Konditionierung der Klebung gemäß DIN EN 1465 bei Raumtemperatur zu 9,5 N/mm2 bestimmt.Gold-plated brass sheet was coated with 5 mg of 5- (p-aminobenzylazo) -8-hydroxyquinoline, dissolved in 200 ml of ethanol, by immersion for 24 hours. Subsequently, silver-filled epoxy adhesive was applied and the tensile strength after evaluation and conditioning of the bond in accordance with DIN EN 1465 at room temperature was found to be 9.5 N / mm 2 .
Beispiel 9: Zugfestigkeitsprobe auf AlMg3 Example 9: Tensile test on AlMg 3
AlMg3 wurde mit 20 mg 5-(p-Vinylbenzylazo)-8-hydroxychinolin, in 250 ml Ethanol gelöst, durch Tauchen während 23 Stunden beschichtet. Anschließend wurde Polyurethan-Gießharz, z.B. Biresin 1305 aufgetragen und die Zugfestigkeit nach Auswertung und Konditionierung der Klebung gemessen, indem die Zugfestigkeit zweier mit den Stirnflächen aufeinander geklebter Rundproben mit 20 mm Durchmesser bestimmt wurde. Die Prüfung bei Raumtempe- ratur ergab eine Zugfestigkeit von 8 N/mm , nach Auslagerung in Wasser bei einer Temperatur oberhalb 95°C während 16 Stunden einen Wert von 4,3 N/mm2, wobei wiederum bei Raumtemperatur gemessen wurde.AlMg 3 was coated with 20 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, by immersion for 23 hours. Polyurethane casting resin, for example Biresin 1305, was then applied and the tensile strength was measured after evaluating and conditioning the bond by determining the tensile strength of two round specimens with a diameter of 20 mm glued to one another with the end faces. The test at room temperature showed a tensile strength of 8 N / mm, after aging in water at a temperature above 95 ° C for 16 hours a value of 4.3 N / mm 2 , again measuring at room temperature.
Beispiel 10: Zugfestigkeitsprobe auf Edelstahl- Werkstoff Nr. 1.4571Example 10: Tensile strength test on stainless steel material No. 1.4571
Edelstahl Nr. 1.4571 wurde mit 20 mg 5-(p-Vinylbenzylazo)-8-hydroxychinolin, in 250 ml Ethanol gelöst, durch Tauchen während 23 Stunden beschichtet. Anschließend wurde Polyurethan-Gießharz, z.B. Biresin U1305 aufgetragen und die Zugfestigkeit wie in Beispiel 9 nach Aushärtung und Konditinierung der Klebung gemessen. Die Messung bei Raumtemperatur ergab eine Zugfestigkeit von 5,1 N/mm2, die Zugfestigkeit nach Auslagerung in Wasser bei einer Temperatur oberhalb von 95°C während 16 Stunden eine Zugfestigkeit von 6,1 N/mm2, wiederum bei Raumtemperatur gemessen. Beispiel 11 : Zugfestigkeitsprobe auf silberbeschichteter KeramikStainless steel No. 1.4571 was coated with 20 mg of 5- (p-vinylbenzylazo) -8-hydroxyquinoline, dissolved in 250 ml of ethanol, by immersion for 23 hours. Polyurethane casting resin, for example Biresin U1305, was then applied and the tensile strength was measured as in Example 9 after the bond had hardened and was conditioned. The measurement at room temperature showed a tensile strength of 5.1 N / mm 2 , the tensile strength after aging in water at a temperature above 95 ° C for 16 hours a tensile strength of 6.1 N / mm 2 , again measured at room temperature. Example 11: Tensile test on silver-coated ceramic
Eine silberbeschichtete Keramik mit 10 mm wurde mit 5-(p-Vinylbenzylazo)-8- hydroxychinolin, wie in Beispiel 10 dargestellt, beschichtet. Nach Aushärtung und Konditionierung der Klebung mit Polyurethan-Gießharz wurde die Zugfestigkeit wie in Beispiel 9 gemessen. Bei Raumtemperatur ergab sich ein Festigkeitswert von 4 N/mm2, nach einer Auslagerung in Wasser bei einer Temperatur oberhalb 95°C über 16 Stunden ein Festigkeitswert von 1,6 N/mm2, wiederum bei Raumtemperatur gemessen.A 10 mm silver coated ceramic was coated with 5- (p-vinylbenzylazo) -8-hydroxyquinoline as shown in Example 10. After curing and conditioning the bond with polyurethane casting resin, the tensile strength was measured as in Example 9. At room temperature there was a strength value of 4 N / mm 2 , after aging in water at a temperature above 95 ° C for 16 hours a strength value of 1.6 N / mm 2 , again measured at room temperature.
Beispiel 12: Zugfestigkeitsprobe auf silberbeschichteter KeramikExample 12: Tensile strength test on silver-coated ceramic
Eine silberbeschichtete Keramik mit 10 mm wurde, wie in Beispiel 10 dargestellt mit 5-(p- Aminobenzylazo)-8-hydroxychinolin beschichtet. Die Zugfestigkeit des Polyurethan- Gießharzes wurde nach Aushärtung und Konditionierung der Klebung gemessen, wie in Beispiel 9 dargestellt. Die Zugfestigkeitsprobe bei Raumtemperatur ergab einen Wert von 5,2 N/mm2; nach Auslagerung in Wasser bei einer Temperatur oberhalb 95°C während 16 Stun- den ein Wert von 2,2 N/mm , wiederum bei Raumtemperatur gemessen.A 10 mm silver-coated ceramic was coated with 5- (p-aminobenzylazo) -8-hydroxyquinoline as shown in Example 10. The tensile strength of the polyurethane cast resin was measured after curing and conditioning the bond, as shown in Example 9. The tensile strength test at room temperature gave a value of 5.2 N / mm 2 ; after aging in water at a temperature above 95 ° C for 16 hours a value of 2.2 N / mm, again measured at room temperature.
Die erfindungsgemäßen Haftvermittler können in sehr geringer Schichtdicke, d.h. ggf. in monomolekularer Schicht auf die metallische Oberfläche aufgetragen werden. Die aufeinanderfolgenden Schichten, nämlich der erfindungsgemäße Haftvermittler direkt auf eine metallischen Oberfläche, eine mit der reaktiven polymerspezifischen Gruppe des Haftvermittlers reagierende Polymerschicht kann beim Aufbau eines elektronischen Bauelementes wiederum mit einer Schicht des erfindungsgemäßen Haftvermittlers, der auf eine metallische Oberfläche geschichtet ist, beschichtet werden. Insgesamt ergibt sich der in den Figuren 5 und 6 dargestellte Aufbau.The adhesion promoters according to the invention can be applied in a very small layer thickness, i.e. if necessary, be applied to the metallic surface in a monomolecular layer. The successive layers, namely the adhesion promoter according to the invention directly on a metallic surface, a polymer layer reacting with the reactive polymer-specific group of the adhesion promoter can in turn be coated with a layer of the adhesion promoter according to the invention, which is layered on a metallic surface, when building up an electronic component. Overall, the structure shown in FIGS. 5 and 6 results.
Dabei ist in Figur 5 die Schicht 1 eine metallische Oberfläche, Schicht 2 die Haftvermittlerschicht und Schicht 3 eine organische Polymerschicht. . -5, layer 1 is a metallic surface, layer 2 is the adhesion promoter layer and layer 3 is an organic polymer layer. , -
In Figur 6 ist Schicht 1 eine metallische Schicht, Schicht 2 die Haftvermittlerschicht, Schicht 3 eine organische Polymerschicht, Schicht 4 eine weitere Haftvermittlerschicht und Schicht 5 eine weitere metallische Schicht.In FIG. 6, layer 1 is a metallic layer, layer 2 is the adhesion promoter layer, layer 3 is an organic polymer layer, layer 4 is another adhesion promoter layer, and layer 5 is another metallic layer.
Die Schichten 1 in Figuren 5 und 6 können auch eine dünne Metallschicht sein, die auf eine Unterlage aufgebracht wurde, wie z.B. eine Gold- oder Silberbeschichtung auf einer Piezoke- ramik.The layers 1 in Figures 5 and 6 can also be a thin metal layer which has been applied to a base, e.g. a gold or silver coating on a piezo ceramic.
Figur 6 zeigt einen Aufbau, bei dem zwei gleiche oder unterschiedliche metallische Oberflächen, die Schichten 1 bzw. 5, mit jeweils einer Schicht des Haftvermittlers bedeckt sind, die an gegenüberliegenden Seiten an eine gemeinsame organische Polymerschicht angrenzen. Die Haftvermittlerschichten 2 und 4 können dabei aus dem gleichen 8-Hydroxychinolinderivat bestehen, oder aus verschiedenen, solange sie nur reaktive Gruppen tragen, die mit mono- oder oligomeren der organischen Polymerschicht 3 reagieren können. Die organische Polymerenschicht 3 kann hier ein Gemisch verschiedener Monomere sein, z.B. Monomeren, die Po- lyesther, Polyurethane, Polycarbonate und/oder Polyamide bilden können.FIG. 6 shows a structure in which two identical or different metallic surfaces, layers 1 and 5, are each covered with a layer of the adhesion promoter which adjoins a common organic polymer layer on opposite sides. The adhesion promoter layers 2 and 4 can consist of the same 8-hydroxyquinoline derivative, or of different ones, as long as they only carry reactive groups that can react with mono- or oligomeric organic polymer layer 3. The organic polymer layer 3 here can be a mixture of different monomers, e.g. Monomers that can form polyesters, polyurethanes, polycarbonates and / or polyamides.
Die in der vorangehenden Beschreibung, in der Zeichnung sowie in den Ansprüchen offenbarten Merkmale der Erfindung können sowohl einzeln als auch in beliebigen Kombinationen für die Verwirklichung der Erfindung in ihren verschiedenen Ausführungsformen wesentlich sein. The features of the invention disclosed in the preceding description, in the drawing and in the claims can be essential both individually and in any combination for realizing the invention in its various embodiments.

Claims

WO 01/09099 _ j j _ PCT/DE00/02481Ansprüche: WO 01/09099 _ jj _ PCT / DE00 / 02481 Claims:
1. 8-Hydroxychinolinderivate, erhältlich durch Azokupplung von 8-Hydroxychmolin mit organischen Diazoniumverbindungen, die mindestens eine weitere zur Polymerisationsreaktion mit organischen Polymeren fähige Gruppe tragen.1. 8-hydroxyquinoline derivatives obtainable by azo coupling of 8-hydroxychmoline with organic diazonium compounds which carry at least one further group capable of polymerizing with organic polymers.
2. 8-Hydroxychinolinderivate nach Anspruch 1, bei denen die azogekuppelten Diazoniumverbindungen aromatisch sind.2. 8-hydroxyquinoline derivatives according to claim 1, wherein the azo-coupled diazonium compounds are aromatic.
3. 8-Hydroxychinolinderivate nach Anspruch 1 oder 2, bei denen die azogekuppelten Diazoniumverbindungen mindestens eine weitere freie Amino-, Carboxy-, Epoxy-, Alkenyl- oder Alkylgruppe tragen.3. 8-hydroxyquinoline derivatives according to claim 1 or 2, in which the azo-coupled diazonium compounds carry at least one further free amino, carboxy, epoxy, alkenyl or alkyl group.
4. 8-Hydroxychinolinderivate nach Anspruch 1, die der folgenden allgemeinen Formel entsprechen: 4. 8-hydroxyquinoline derivatives according to claim 1, which correspond to the following general formula:
wobei R = aliphatischer oder aromatischer Kohlenwasserstoff mit 2 bis 6 C-Atomen ist, der mindestens einen reaktiven Substituenten trägt.where R = aliphatic or aromatic hydrocarbon with 2 to 6 carbon atoms, which carries at least one reactive substituent.
5. 8-Hydroxychinolinderivate nach Anspruch 4, bei dem der Substituent eine Amino-, Epoxy-, Alkenylgruppe oder Hydroxygruppe ist. 5. 8-hydroxyquinoline derivatives according to claim 4, wherein the substituent is an amino, epoxy, alkenyl group or hydroxy group.
6. Verfahren zur Herstellung von 8-Hydroxychinolinderivaten, dadurch gekennzeichnet, daß 8-Hydroxychinolin mit einer organischen Diazoniumverbindung umgesetzt wird, die mindestens eine weitere zur Polymerisation fähige Gruppe enthält.6. A process for the preparation of 8-hydroxyquinoline derivatives, characterized in that 8-hydroxyquinoline is reacted with an organic diazonium compound which contains at least one further group capable of polymerization.
7. Verfahren nach Anspruch 6, bei dem die organische Diazoniumverbindung aromatisch ist.7. The method of claim 6, wherein the organic diazonium compound is aromatic.
8. Verfahren nach Anspruch 6 oder 7, bei dem die zur Polymerisation fähige Gruppe der organische Diazoniumverbindung eine weitere Epoxy-, Carboxy-, Alkenyl- oder Amino- gruppe enthält.8. The method according to claim 6 or 7, wherein the polymerizable group of the organic diazonium compound contains a further epoxy, carboxy, alkenyl or amino group.
9. Verfahren nach einem der Ansprüche 6 bis 8, bei dem eine Mischung organischer Diazo- niumverbindungen eingesetzt wird.9. The method according to any one of claims 6 to 8, in which a mixture of organic diazo nium compounds is used.
10. Verwendung eines 8-Hydroxychinolinderivates nach einem der vorangehenden Ansprüche als Haftvermittler zwischen einer metallischen Oberfläche und einer organischen Polymerschicht. 10. Use of an 8-hydroxyquinoline derivative according to any one of the preceding claims as an adhesion promoter between a metallic surface and an organic polymer layer.
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AU6981600A (en) 2001-02-19
NO20020436D0 (en) 2002-01-28
AU774023B2 (en) 2004-06-10
WO2001009099A3 (en) 2001-06-07
NO20020436L (en) 2002-01-28
NO321886B1 (en) 2006-07-17
ZA200200805B (en) 2003-06-25
EP1200408B1 (en) 2003-09-03
DE50003566D1 (en) 2003-10-09
ATE248820T1 (en) 2003-09-15

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